Printing medium comprising aerogel materials

ABSTRACT

New aerogels are disclosed which comprise silica, at least one organic polymer having polar functional groups, and at least one metal ion. Also disclosed are methods for making such aerogels. The present invention further concerns printable objects comprising these aerogels, specifically when the print media are imaged by the absorption of liquid and the spatial localization of pigments or dyes.

CROSS REFERENCES TO RELATED APPLICATIONS

The present application is a continuation of U.S. Ser. No. 09/928,961,filed Aug.13, 2001 (now U.S. Pat. No. 6,602,336), which claims priorityfrom U.S. application Ser. No. 09/130,943, filed Aug. 7, 1998 (now U.S.Pat. No. 6,303,046), which claims priority to U.S. ProvisionalApplication Ser. No. 60/085,469, filed May 14, 1998 and U.S. ProvisionalApplication Ser. No. 60/055,146, filed Aug. 8, 1997.

FIELD OF THE INVENTION

The present invention relates to printing medium and materials based onaerogels that comprise silica, a particular class of polymers, and atleast one metal ion. The invention also relates to various methods forproducing the aerogels of this invention. In addition, the presentinvention pertains to numerous applications and devices utilizing thenew aerogels.

BACKGROUND OF THE INVENTION

An aerogel is a gel which has a lower density than the fully condensedform of the material comprising the gel. Aerogels typically are producedby replacing the liquid of a gel by air or another gas without allowingcomplete collapse of the structure. The seminal report on this was madeby Kistler in 1931 (Nature, 127, 741(1931)), who described the goal ofthe research as being “to test the hypothesis that the liquid in a jellycan be replaced by a gas with little or no shrinkage”. This early workled to aerogels through the use of supercritical fluids to extractliquid, and it led to the hypothesis that the gel structure itself canbe preserved in the supercritical drying process, as disclosed byMarshall in U.S. Pat. No. 285,449 (1942).

There have been many successes in the aerogel field, as disclosed in thescientific and technical literature and in patents. Of relevance to thecurrent invention is the area known in some contexts as OrganicallyModified Ceramics, referred to as ORMOCERS or called CERAMERS, whichhave been widely studied. A descriptive review of this area is that ofR. C. Mehrotra (Present Status and Future Potential of the Sol-GelProcess, Chapter 1 in Chemistry, Spectroscopy and Applications ofSol-Gel Glasses, Structure and Bonding Series 77, Eds. R Reisfeld and C.K. Jorgensen, Springer-Verlag, Berlin, 1992). This reference points tothe distinction between composite materials that are mixed at themolecular level and those that have mechanically combined components.This reference also discusses work directed to organically modified gelsin the form of aerogels and their subsequently dried, fused, oxidizedand otherwise treated forms. Also of relevance are works concerningaerogels and their applications. The book Aerogels edited by J. Fricke(Springer Proceeding in Physics 6, Springer-Verlag, Berlin, 1985), thebook Sol-Gel Science, The Physics and Chemistry of Sol-Gel Processing byC. J. Brinker and G. W. Scherer (Academic Press, Inc. Harcourt BraceJovanovich, Publ., New York, 1990) and the book Sol-Gel Technology forThin Films, Fibers, Preforms, Electronics and Specialty Shapes, Ed. L.C. Klein (Noyes, Park Ridge, N.J., 1988) are of relevance and show thegreat importance attached to the formation of aerogels with specificproperties and functions. U.S. Pat. No. 4,440,827 discloses in claim 13the use of silica particles in media for ink jet recording and opticalbar code printing, wherein one of the methods for preparing thesynthetic silica that may be used is an aerogel process. The use ofsilica aerogel in Cerenkov detectors is described, for example , by M.Cantin, L. Koch, R. Jouan, P. Mestreau, A. Roussel, F. Bonnin, J. Mouteland S. J. Tiechner, in their paper in Nuclear Instruments and Methods,118, 177 (1974).

Examples of aerogels which contain or have added to them, metal ions ormetal containing species are well known. Those known fall into severalcategories, including: (1) a silica aerogel that has been dipped into asolution or dispersion containing the metal ion source; (2) a polymermatrix aerogel, such as a polyacrylonitrile aerogel, that contains metalions added to the aerogel or to the gel before formation of the aerogel(e.g. L. M. Hair, L. Owens, T. Tillotson, M. Froba, J. Wong, G, J.Thomas, and D. L. Medlin, J. Non-Crystalline Solids, 186, 168 (1995),and S. Ye, A. K. Vijh, Z-Y Wang, and L. H. Dao, Can. J. Chem. 75, 1666(1997)); or (3) a silica aerogel having metal ions (e.g. M. A. Cauqui,J. J. Calvino, G. Cifredo, L. Esquivias, and J. M. Rodriguez-lzquierdo,J. Non-Crystalline Solids, 147&148, 758 (1992)) or small metal compoundsbound in it (e.g. Y. Yan, A. M. Buckley and M. Greenblatt, J.Non-Crystalline Solids, 180, 180 (1995)).

The use of supported metal and metal ions for catalysis is widely knownand practiced, and many reports exist in the scientific, technical,engineering, and patent literature. Relevant studies include “TheChemistry of Ruthenium in PSSA lonomer: Reactions of Ru-PSSA with CO, H₂and O₂ and Alcohols” (I. W. Shim, V. D. Mattera, Jr., and W. M. Risen,Jr., Journal of Catalysis, 94, 531 (1985), which includes a report of astatic Fischer—Tropsch reaction catalysis by supported ruthenium undermild conditions of 150° C. and 600 Torr total pressure, “A Kinetic Studyof the Catalytic Oxidation of CO over Nafion-Supported Rhodium,Ruthenium, and Platinum”, by V. D. Mattera, Jr., D. M. Barnes, S. N.Chaudhuri, W. M. Risen, Jr., and R. D. Gonzalez, Journal of PhysicalChemistry, 90, 4819 (1986), which shows this catalysis, and “Chemistryof Metals in lonomers: Reactions of Rhodium-PSSA with CO, H₂, and H₂O”,Inorganic Chemistry, 23, 3597 (1984), which shows relationships betweenspectroscopic observations on supports that have been exposed to thesegases and the compounds formed and the oxidation states of rhodiumspecies.

Despite the known aerogels and metal supports, a need still remains forimproved aerogels and related materials having superior properties andapplicability.

SUMMARY OF THE INVENTION

In a first aspect, the present invention provides a new and uniqueprinting medium that comprises an aerogel which includes silica, atleast one polymer having a polar functional group, and at least onemetal-ion-containing species.

In yet another aspect, the present invention provides a medium forprinting that comprises an aerogel comprising silica and an organicpolymer.

Further scope of the applicability of the present invention will becomeapparent from the detailed description given hereinafter. It should,however, be understood that the detailed description and specificexamples, while indicating preferred embodiments of the invention, aregiven by way of illustration only, since various changes andmodifications within the spirit and scope of the invention will becomeapparent to those skilled in the art.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1 a to 1 f illustrate the ultraviolet-visible range spectrum ofvarious silica-chitosan-M aerogels in accordance with a preferred aspectof the present invention;

FIGS. 2 a to 2 e illustrate the near infrared range spectra of varioussilica-chitosan-M aerogels in accordance with a preferred aspect of thepresent invention;

FIG. 3 illustrates the infrared spectra of a silica-chitosan rhodiumaerogel, presented as absorbance as a function of wave number, beforeand after exposure to CO; and

FIG. 4 illustrates the infrared spectra of a silica-chitosan-rutheniumaerogel, presented as absorbance as a function of wave number, beforeand after exposure to NO.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention concerns printing mediums that include newaerogels that comprise silica, at least one organic polymer having polarfunctional groups, and at least one metal ion. More particularly, theinvention concerns printing mediums based upon aerogels that comprise anorganic polymer that interacts with the metal ion through ionic,coordinate covalent, or covalent bonds. The invention also concernstransparent aerogel monoliths comprising silica, an organic polymerhaving polar functional groups, and a metal-containing species. Thepresent invention also provides a process for producing some of thesenovel materials, in which the silica source, the organic polymer, ametal ion containing source, and liquid form a clear gel. In accordancewith this process, the gel may be placed in a liquid extractable form byreplacing the liquid with an alcohol in the gel without removing theconstituents completely, and then the alcohol and remaining liquid areextracted from the gel by supercritical extraction using carbon dioxide.This process can include an adjustment of the pH of the system at eachstage to control the rate of gelation and the sol-gel morphology, or tocontrol the solubility, configuration and metal ion coordinatingcapability of the polar functional polymer. The present inventionprocess can be carried out in stages such that the silica source and thepolar functional organic polymer form a clear sol which then forms aclear gel, which may be treated to adjust the pH. The wet gel is thenreacted with a metal ion source to form a clear gel, the gel liquid isthen replaced with alcohol. A supercritical extraction operation iscarried out to provide a monolithic aerogel.

These monolithic aerogels in accordance with the present inventionpossess a number of properties that lead to novel applications. Theyhave high surface areas and high void volumes related to their lowdensities. Monolith is a word used in its conventional sense, as “asingle stone or block of stone” (Webster's New Collegiate Dictionary),in order to distinguish the materials of this invention (before anyintentional fracturing, powdering or other mechanical processes) fromthe types of small particles or aggregate particles commonly obtained inthe prior art. Typically, the monoliths obtained are limited only by thesize of the supercritical extraction equipment and pieces as large asabout 50 mm×50 mm have been prepared. Their thicknesses may typicallyvary from about 0.02 mm to about 4 mm. Greater or lesser thicknesses arecontemplated. The monolithic structure permits applications of thesematerials as optical elements of low refractive index, optical filters,gas and liquid absorbent materials, gas filters, as well as those thatare possible with the smaller particles.

The term “polymer” as utilized herein generally refers to amacromolecular substance composed of repeating atomic groups, i.e.monomers. The term encompasses all types of polymers such ashomopolymers, copolymers, dimers, trimers, oligomers, for example.

The aerogels of the present invention may comprise metal ions that caninteract with reactive gases and unreactive but absorbable gases toyield a changed material whose changes can be probed to indicate thepresence of the molecules. The aerogels may comprise metal ions that caninteract with many dye molecules to immobilize them by a mordantinginteraction. Moreover, the aerogels can be transparent to light inregions of interest, such that they may be used as optical filters,active optical elements, and detectors based on the optical, magnetic,and magneto-optic and related properties of the metals and theirsurroundings. The aerogels of the present invention have pore sizes inthe range of about 2 to about 6 nanometers, very high surface areas, andmay comprise metals that exhibit appropriate molecule—metal interactionsand chemical reactions for catalytic activity.

It has been discovered that certain organic polymers with polarfunctional groups are particularly useful constituents in such aerogels.These preferred organic polymers can be dissolved in the solution inwhich the silica source is provided, which form with the silica source,a clear sol and subsequent gel, which can be placed in a chemical formthat leads to interaction with the metal ions at a pH at which thesilica network is stable, and which are not extracted to a deleteriousextent by interactions with solutions, liquids, or supercritical fluidin the preparation process. For the case in which the silica source isan alkoxide, such as tetraethyl orthosilicate (TEOS), formation of amonolithic gel occurs preferably under acidic conditions with water andalcohol present. Note that TEOS can also be written as tetraethoxysilane, and it belongs to the class that includes tetraalkoxysilanes ingeneral, trialkoxy alkyl silanes, dialkoxy dialkyl silanes and otherclosely related compounds, which can hydrolyze to give 2,3, or 4 hydroxygroups with which to form part or all of a silica network, such as wouldbe well known to one reasonably skilled in the art. Other alternatesilica sources could be employed. Thus, the preferred organic polymermust have sufficient solubility to permit its incorporation in the soland not precipitate to produce a visual cloudiness during gelation.Moreover, it must form a sufficiently strong interaction with the otherconstituents of the gel such that it is not extracted to a deleteriousextent by solutions used to introduce the metal ion containing speciesand so that it is not extracted to such an extent by alcohol that isused to replace other liquids in preparation for the supercriticalextraction. Finally, the preferred organic polymer must have thefunctionality necessary to interact with the metal ion containingspecies under conditions, such as conditions reflected by pH ortemperature, in which both the silica and the polymer is chemicallystable.

A preferred organic polymer that has these characteristics is chitosan,which is the name given to materials derived from chitin by deacylation.These materials vary in degree of deacylation and molecular weightaccording to the source of the chitin and the deacylation process.Commercial chitosan typically is prepared from chitin from the skin orshell of anthropods and thus often is a recovered waste product of thefishing industry. Chitosans in the range of 50 to 100% deacylated(replacement of 50 to 100% of acylamine groups by amine groups) andmolecular weights in the 35,000 to 3,000,000 Dalton can be used. Morepreferred are chitosans in the range of weight average molecular weightsof 150,000 to 2,500,000 g/mol and degrees of deacylation from about 70to about 100%. Most preferred are chitosans with such weights of 300,000to 2,100,000 g/mol and degrees of deacylation from about 80 to about100%.

Chitosan is a copolymer containing bothbeta-(1-4)-2-acetamido-2-deoxy-D-glucose andbeta-1(1-4)-2-amino-2-deoxy-D-glucose units. The amine group of thedeacylated units can form coordinate covalent bonds to metal ions bycomplexation. The extent to which the amine group, which coordinates tometal ions, is present relative to its protonated form depends on the pHof the system. A characteristic of chitosan that is unusual forcompounds with primary amine groups is that the pKa is about 6.3. Thismeans that a significant fraction of the groups are in the amine form atpH less than 7. Furthermore, this also means that chitosan cancoordinate effectively at pH less than 7 rather than at the higher pHvalues at which the silica network is subject to base hydrolysis andinstability.

Another characteristic of chitosan is that it has OH groups. Withoutbeing limited to any particular theory, it is contemplated that the OHgroups assist in the interaction of the polymer with the silica as it ispresent in the various stages of preparation and in the final form ofaerogel material. This characteristic as well as the interactions ofother groups of the chitosan copolymer with the silica, and of the OHgroups with the metal ions and with other chitosan units may be thereason that the polymer is not extracted to a deleterious extent whenthe wet gel is exposed to aqueous metal ion containing solutions andalcohols.

Other organic polymers suitable for forming the aerogels of thisinvention include, but are not limited to, alginic acid, gelatin, pecticacid (from apples), carboxylate-modified poly(acrylamide), carboxylatemodified chitosan, polyvinyl alcohol that is about 100% hydrolyzed andof weight average molecular weight in the 100,000 to 200,000 range,poly(acrylic acid). Other carbohydrates with polar groups, such ascarrageenans, modified starches such as amylopectin, epichlorohydrin oralkyene oxide modified amylopecin and certain dextrins. Clearly polymerssuch as polyamines and others fulfilling the role of the polymer butwhose polar groups are thiol, thioether, phosphate, also could be usefulin the formation of these aerogels using the methods of the invention.

It has been discovered that the aerogels of this invention can befriable so that they are easily broken into relatively small pieces foruse as particles. The minimum particle size is about 25 nanometers. Whenthis property is combined with the ability to absorb liquids containingdyes, the aerogel of this invention provides a novel particle for use onor as part of imaging surfaces such as those imaged with solvent borneinks. When the friability is combined with the inclusion ofcatalytically useful metal ions and the reduction, oxidation and otherreaction products, the aerogel of the present invention can be used as acatalyst agent or as a vehicle therefor.

Another important feature of the aerogels of the present invention istheir transparency to light in certain wavelength regions. This feature,particularly when taken on combination with the high surface areas andreactive metal ions and absorptive structure of the aerogels, hasprovided a wide array of novel uses for the aerogels as detectionelements and optical elements. This transparency is immediately evidentin certain regions of the visible spectrum, at which they are coloredbut relatively transparent, resembling pieces of colored but clearglass. Absorption of gases by the aerogels can cause a color change inthe aerogel. Representative examples of gases that may be absorbed bythe aerogels of the present invention, include but are not limited to,CO, H₂, H₂O, NH₃, CO₂, N₂O₄, NO, and NO_(x). Thus, gas absorption can bedetected using the aerogel as the detection element and a suitable lightsource and detector. Absorption of gases which cause changes to theinfrared or near infrared spectrum of the aerogels in the region wherethe aerogels have a spectral transmission of greater than about 10%provides an element for a detector for those gases. It has beendiscovered that detection of CO, NO, and N₂O₄ with detection in the midinfrared region provides a detector element for these gases.

The monolithic aerogels of the invention have high porosity and surfacearea and comprise metal containing species, such as metal ions. Arepresentative listing of suitable metal ions includes, but is notlimited to, Co, Cu, Fe, Cr, Ni, Mn, Rh, Ru, Ir, Pd, Pt, Yb, Er, Eu, Sm,and Dy. The metal ions can be selected from those that interact withselected impurities in a gas or gas stream and remove or transform them.Thus, the invention of the aerogels as gas absorber in a setting where amonolithic material is required is exemplified by the absorbance of NOby a ruthenium—containing chitosan silica aerogel.

The present invention is further illustrated by the following examples.It is to be understood that the present invention is not limited to theexamples, and various changes and modifications can be made in theinvention without departing from the spirit and scope thereof.

EXAMPLES Example 1

A mixture of 12.5 mL of tetraethylorthosilicate (TEOS), 40 mL of anaqueous solution containing 1 wt % of 80% deacylated chitosan (suppliedby Fluke, molecular weight of 2,000,000) and 1 wt % acetic acid, and 0.9mL of glacial acetic acid was prepared, and stirred at room temperature(about 25° C.) for 6-9 hours. A clear, colorless and viscous sol formed,and a portion of it was poured into a polystyrene box. The box isapproximately 2 in.×2 in. and about 1 in. high. The sol was poured intothe box to a depth of about 1 to 2 mm., and the lid was placed on thebox. This film was allowed to gel and then to age overnight. Then about10 mL of a solution of absolute ethanol and ammonium hydroxide was addedto the gel. The solution contained the amount of ammonium hydroxiderequired to adjust the pH of the solution, once in contact with the gel,to about 7.0. (Note that even though the solution added was alcohol, thesolution present after solvent exchange and neutralization was waterbased, so the pH value is a valid parameter.) After this wasaccomplished, the supernatant solution was replaced with absolutealcohol, the lid was replaced, and the alcohol remained in contact withthe wet gel for a few hours. This was repeated at least four times overseveral days to produce a wet gel in which the liquid was nearly allethanol.

Example 2

The wet gel produced in Example 1 was placed in the pressure vessel of asupercritical fluid extractor, and the solvent was extracted with carbondioxide (CO₂) under supercritical conditions, which reached 1400 psi and35° C. The result was a clear, hard, brittle monolithic aerogel, whichcan be labeled Si—X, for silica and chitosan containing material. Itsdensity was found to be 0.25 g/cm³, and it BET surface area was found tobe 673 m²/g.

Aerogels of this type with the chitosan to silica dry weight ratios of5:95, 10:90, and 20:80 were prepared. These aerogels utilized chitosanmaterials of molecular weights 2,000,000; 750,000; and 70,000.

Example 3

A wet gel produced as in Example 1 was treated to one more step, inwhich the supernatant ethanol was replaced by a solution made bydissolving a compound of a transition metal in ethanol. The lid wasplaced on the box, and the interaction between the gel and solution wasallowed to proceed for three days. Thus, one gel was treated with onesolution. Then the wet gel was processed by supercritical fluidextraction, as described above, to produce a metal-ion-containingaerogel. In this example, the metal ion containing compound was 0.01 MRhCl₃, and the final aerogel was a thin clear, yellow-orange monolithicsolid. Its density was found to be 0.27 g/cm³, and its BET surface areawas found to be 555 m²/g. Its refractive index was measured at 632.8 nmusing a Metricon 2010 Prism Coupling Instrument (Metricon Corporation)and found to be 1.17. This aerogel is labeled Si—X—RhCl₃ (or Si—X—RhCl₃(0.01M).

Aerogels containing other metals were prepared. They were prepared withtreatment solution concentrations ranging from 0.001 to about 0.1 M,with a range of chitosan to silica dry weight ratios. The compounds usedfor treatment included the following: rhodium trichloride, rutheniumtrichloride, molybdenum trichloride, cobalt (II) acetylacetonate(Co(acac)₂), Ni acetylacetonate (Ni(acac)₂), cobalt chloride, cobaltnitrate, silver nitrate, copper chloride, manganous chloride,chloro-1,5-cyclooctadiene iridium(I) dimer,and palladium chloride.Nickel nitrate and nickel chloride could also be used.

These aerogels exhibited similar properties. For example, the density ofthe SiO₂—X—RuCl₃ (0.02M) aerogel, prepared using a 0.02 M RuCl₃ wasfound to be 0.27 g/cm³, its BET surface area was 494 m₂/g, and itrefractive index at 632.8 nm. was found to be 1.17. As another exampleof this type, SiO₂—X—Co (0.01M) had a density of 0.26, a BET surfacearea of 500 m²/g, and a refractive index at 632.8 nm of 1.14. All of theaerogels could be obtained as clear, hard, brittle monolithic pieces.All BET surface areas obtained were in the 382 to 957 m²/g range, anddensities in the 0.15 to 0.32 g/cm³ range.

Example 4

A mixture of 3.1 mL of tetraethylorthosilicate (TEOS), 10 mL of anaqueous solution containing 1 wt % of 80% deacylated chitosan and 1 wt %acetic acid, and 0.2 mL of glacial acetic acid was prepared, and stirredat room temperature (about 25° C.) for 6-9 hours. During the initialstage of stirring, 2.5 mL of an aqueous solution of potassiumtetrachloroplatinate was added drop by drop very slowly. The amount ofpotassium tetrachloroplatinate added was one Pt per eight amine groupsof chitosan. During the stirring for 7 hours, the viscosity increasedand the color of the clear gel became a bright yellow. Once this sol wasformed, a portion of it was poured into a polystyrene box. The box isapproximately 2 in.×2 in. and about 1 in. high. The sol was poured intothe box to a depth of about 1 to 2 mm., and the lid was placed on thebox. This film was allowed to gel and then to age overnight. Then about10 mL of a solution of absolute ethanol and ammonium hydroxide was addedto the gel. The solution contained the amount of ammonium hydroxiderequired to adjust the pH of the solution, once in contact with the gel,to about 7.0. After this was accomplished, the supernatant solution wasreplaced with absolute alcohol, the lid was replaced, and the alcoholremained in contact with the wet gel for a few hours. This was repeatedat least four times over several days to produce a wet gel in which theliquid was nearly all ethanol. The wet gel produced was placed in thepressure vessel of a supercritical fluid extractor, and the solvent wasextracted with carbon dioxide (CO₂) under supercritical conditions.

Example 5

A SiO₂—X—Rh(III) aerogel sample was placed in a cell for measuring itsinfrared spectrum and controlling the surrounding atmosphere. The cellbody was made of glass, and the windows were made of potassium bromidecrystals. The air in the cell was pumped out and the infrared spectrumof the aerogel film was measured. Then, carbon monoxide (CO) wasadmitted to the cell at a pressure of 0.1 atmosphere. After about 30minutes the CO was evacuated and the infrared spectrum of the exposedaerogel was measured. It showed the presence of three new infraredabsorption bands, at 2032 and 2090, and at 2137 cm−1. The first two areassigned to a Rh(I)(CO)₂, or rhodium(I) dicarbonyl species, as shown inthe paper A Kinetic Study of the Catalytic Oxidation of CO overNafion-Supported Rhodium, Ruthenium and Platinum, V. D. Mattera, Jr., D.M. Barnes, S. N. Chaudhuri, W. M. Risen, Jr. and R. D. Gonzalez, J.Physical Chemistry, 90, 4819(1986). The third band is due to physicaladsorption of the CO by the aerogel. These results are that the aerogeladsorbs CO and that it reacts with it in a manner that is detectable byinfrared spectroscopy. In addition, it shows that some of the Rh(III)was reduced to Rh(I).

Example 6

Example 5 was repeated but the CO gas was replaced with NO, and theresult was the appearance of an infrared band at 1727 cm−1.

Example 7

Example 5 was repeated but the aerogel was SiO₂—X—RuCl₃. The infraredspectrum showed new bands at 1968, 2018, 2080, and 2144 cm−1. The firstis assigned to a Ru(II) carbonyl, the next two to a Ru(lII) carbonyl andthe last to physically absorbed CO, based on the paper.

Example 8

Example 6 was repeated but the aerogel was SiO₂—X—PdCl₂ and theinteraction with NO gas produced new infrared bands at 1820 and 1858cm−1.

Example 9

In a typical preparation of an aerogel based on a carboxylic acidcontaining polymer, 40 mL of a 1 wt. % pectic acid aqueous solution atpH4 was combined with 7.6 mL tetramethylorthosilicate (TMOS) at about25° C. After about 10 min of stirring, the solution became clear andhomogeneous. After being stirring for an additional 1.5 hours, thesolution was placed in a polystyrene box, of the type described above.About 4 mL of solution was placed in each box, and the lid was placed onthe box. The sol aged overnight to form a clear colorless gel. Then thereaction of these films with various metals was carried out by placingthe solutions containing the metal ion in contact with the wet gel. Thenthe gel liquid was replaced in stages beginning with a solution that was3:1, V/V water to ethanol and ending with alcohol. Finally, the wet gelcontaining ethanol as its primary liquid had the liquid extracted bysupercritical fluid extraction with CO₂. This method was used to prepareaerogels comprising Er(III), Yb(III), Sm(III), and Dy(III) In severalcases, two or more lanthanide metal ion containing compounds were addedtogether. For example, Yb(III) and Er(III) were so combined. Aerogelmonoliths were obtained.

Example 10

A sample of the SiO₂—X aerogel based on 10:90 ratio, was touched with adrop from a micropipet of each of the following dyes and ink, selectedto have a range of colors, solvent and molecular type: eriochrome blackT in methanol, phenyl red in water, crystal violet in water, malachitegreen in water, methyl red in ethanol, and standard pen recorder blue(for Hewlett Packard pen recorder). For comparison, the same experimentwas done with a piece of SiO₂—X—Cu aerogel, SiO₂-pectic acid-Yb aerogel,SiO₂—X—Co aerogel, and SiO₂—X—Ni aerogel, as well as a piece of aerogelmade without either the organic polymer or the metal ion containingspecies, which will be labeled “SiO₂ aerogel prep”. The results were asfollows. The ink and dyes were taken up very fast by the aerogels. Thedrops dried very fast in terms of spread of the image, such that theshape of the image was essentially the of the drop and its placement onthe aerogel monolith. By using aerogel monoliths of about 0.3 mmthickness, it was possible to make the foregoing observations concerninglateral spread, but also about spread through the thickness and theeffect on transparency. The with small drop sizes relative to thethickness of the monoliths, the whole drop could be absorbed withoutnoticeable spread laterally and without penetrating to the back side ofthe aerogel through its thickness. In addition, the interaction of thedye solutions and ink with the aerogels was found to be observablethrough the still transparent samples. The colors of the dyes asabsorbed are given in Table 1.

TABLE 1 chloro phenyl eriochrome crystal methyl blue pen malachitephenyl red red black T violet red recorder green (in H₂O) (in H₂O) (inCH₃OH) (in H₂O) (in EtOH) ink (in H₂O) SiO₂ brownish red yellow burgundypurple red green aerogel orange blue SiO₂- dark brown red black purplered green chitosan blue aerogel SiO₂- black deep brick black-violetviolet pink-orange blue chitosan- red Co SiO₂- brown orange black violetpink deep blue blue chitosan- green Cu SiO₂- black red violet violetpale red blue chitosan Ni Aerosil brown orange brownish red purple redgreen 200 red blue Degussa com'cl Lot No: c/2/30c TLC brown orange browndeep purple red green plate red

Example 11

Samples of powder of the SiO₂ aerogel prep, SiO₂—X aerogel, SiO₂ from astandard thin layer chromatography (tic) plate, and SiO₂ aerosil(Degussa Aerosil 200, Lot c/2/30c), and of SiO₂—X—Cu aerogel. The uptakeof the solutions to apparently dry particles was instantaneous with theaerogels prepared with a chitosan to silica dry weight ratio of 10:90 asexamples of this invention. It was observed to be much faster than theup take by the Degussa Aerosil 200. The results also are included inTable 1.

Example 12

Samples of the particles of Example 11 were dispersed in a solution ofpolyvinyl alcohol (100% hydrolyzed, molecular weight 115,000, Cat. #002from Scientific Products), and cast onto microscope slides, and dried atabout 70° C. for about 10 minutes. Then drops of the dye solutions wereapplied to these films. The aerogels of this invention took up the dyeswith essentially the same colors as observed on the monoliths and did sofaster and with greater control of lateral spread than either the silicagel from the tic plate or the Degussa aerosil.

Example 13

A powdered sample of SiO₂—X—Co(II) aerogel was powdered and placed in aglass tube and studied by electron spin resonance spectroscopy.Similarly, the esr spectrum of the SiO₂—X—Rh(III) and SiO₂—X—Ru(III)materials were studied. In all cases, the esr spectra characteristic ofthe metal ions in their environment and oxidation state were observed.

Example 14

A monolith of SiO₂—X—Co(II) was placed in a glass cell consisting of aglass tube with glass windows attached to the ends and a stopcockattached to the side, and the cell was evacuated at 25° C. and thevisible spectrum was measured in transmission. Then the sample wasexposed to the vapors of water. The evident color change was recordedspectroscopically. This experiment was repeated with SiO₂—X—Cu(II)aerogel and the dried material was exposed to water vapor. The evidentcolor change was recorded spectroscopically. The result in the visibleregion of exposing SiO₂—X—Ru(III) to CO is a color change from the redof the original material to a light yellow.

Example 15

A piece of SiO2—X aerogel was placed in a 0.01M nickel nitrate solutionin ethanol. It was removed after about 10 seconds and then it wasallowed to dry in the air. Then it was rinsed by dipping it into ethanolfor about 3 seconds. The light green color of the gel showed that it hadabsorbed nickel ions.

Example 16

A piece of each of the following SiO₂—X—M aerogels, those of Er(III),Yb(III), and Sm(III)measuring about 1 cm by 2 cm, was placed in afurnace in the air and heated to 800° C. The aerogels collapsed to formdense glassy materials.

Example 17

A SiO2—X—Rh(III) aerogel was placed in a cell and dehydrated in vacuo at95° C. for 10 hours, and then exposed to CO gas for about 1.5 hours at0.5 atm. pressure. The infrared spectrum was measured. After subtractionof the spectrum of the background, the spectrum showed bands at 1821,2025, 2097, and 2138, and a shoulder at about 2000 cm⁻¹, which arebelieved to be due to bridging CO on Rh(0) (1821), terminally bound COon reduced (Rh(0)) (2000), terminally bound CO on Rh(I) (2025, 2097),and physically absorbed CO (2138).

Example 18

A sample of SiO₂—X—Rh(III) aerogel was dehydrated at 95° C. in vacuo andtreated with H₂ at 100° C. and 0.5 atm. for about 2 hours. Then it wasreacted with CO at 0.3 atm. for 1.5 hours. The infrared spectrum of theproduct, less that of the dehydrated material, exhibited bands at 1824,2002, 2022, and 2082 cm⁻¹, which are believed to be characteristic of COon Rh(0) and Rh(I). No bands were observed in the region 2100 to 2200,which is the region in which a band for CO absorbed on the originalmaterial containing Rh(III) was seen.

Example 19

A SiO₂—X—Rh(III) aerogel was analyzed to determine the Rh(III) loading.One piece of the aerogel was studied by thermogravimetric analysis, andit was found that 15% of the mass was lost on heating the material underinert gas flow from 25 to 300° C. Another piece was decomposed in strongbase (NaOH). The basic solution was neutralized with HCl, taken to pH 3with HCl, filtered and diluted quantitatively. Its spectrum was measuredin the UV-visible region and compared to a calibration based on rhodiumchloride solutions in HCl solution. These results were combined to yielda value of 3% (w/w) for Rh(III).

Discussion of the Examples

Two processes for making monolithic aerogels comprising silica, a polarfunctional organic polymer, and a metal-ion-containing species have beendescribed. The compositions containing the polar functional organicpolymer, such as an amine functional polymer, form aerogels that areclear, transparent, hard, brittle, and friable with transition metals.The aerogels comprising lanthanide ions were prepared using thecarboxylate functional polymer. Additional preparations were made usingpolymers selected from poly(acrylic acid), alginic acid, gelatin,carboxylate modified poly(acrylamide).

FIG. 1 shows the ultraviolet-visible range spectra, presented inabsorbance as a function of wavelength in the 300–820 nm range, of 0.3mm thick (T=0.3 mm) monolithic pieces of silica-chitosan-metal aerogelsin accordance with a preferred embodiment of the present invention. FIG.1 a is a sample comprising rhodium ions with the source of Rh havingbeen rhodium trichloride; 1 b is a sample comprising nickel ions withthe source of Ni having been nickel nitrate; 1 c is a sample comprisingruthenium ions with the source of Ru having been ruthenium chloride; 1 dis a sample comprising copper ions with the source of Cu having beencopper chloride; 1 e is a sample comprising cobalt ions with the sourceof Co having been cobalt nitrate; and 1 f is a sample comprising cobaltions with the source of Co having been cobalt acetate.

FIG. 2 shows the near infrared range spectra, presented in transmittance(percent transmission) as a function of wavelength in the 700-3100 nmrange, of 0.3 mm thick (T=0.3 mm) monolithic pieces of a silica-chitosanaerogel and silica-chitosan-metal aerogels in accordance with thepreferred embodiment of the present invention. FIG. 2 a is a samplecomprising ruthenium ions with the source of Ru having been rutherniumtrichloride; 2 b is a sample of the silica-chitosan aerogel with nometal ions; 2 c is a sample comprising nickel ions with the source of Nihaving been nickel acetylacetonate; 2 d is a sample comprising cobaltions with the source of Co having been cobalt acetate; and 2 e is asample comprising rhodium ions with the source of Rh having been rhodiumchloride.

FIG. 3 shows the infrared spectra, presented as absorbance as a functionof wave number in the 1450–2350 wave number (1/cm) region, of (a) amonolithic 0.2 mm thick piece of a preferred embodimentsilica-chitosan-rhodium aerogel dehydrated at 95° C. and 0.001 Torrpressure for 10 hours, and (b) the same sample after exposure to CO at380 Torr at 25° C. for 1.5 hours followed by evacuation of the samplechamber to 0.001 Torr for 1 hour. The absorbance scales are offsetarbitrarily for display.

FIG. 4 shows the infrared spectra, presented as absorbance as a functionof wave number in the 1450–2350 wave number (1/cm) region, of (a) amonolithic 0.2 mm thick piece of a preferred embodimentsilica-chitosan-ruthenium aerogel dehydrated at 95° C. and 0.001 Torrpressure for 10 hours, and (b) the same sample after exposure to NO at76 Torr at 25° C. for 10 minutes followed by evacuation of the samplechamber to 0.001 Torr for 0.5 hour. The absorbance scales are offsetarbitrarily for display.

The absorption of gases from an atmosphere has been demonstrated for thecase of CO and NO. Once absorbed, the gases can undergo furtherreactions, as demonstrated in the case of metal ion reduction forRh(III) to Rh(I) and Ru (III) to Ru(II). These are typical reactions forcatalysts that are useful in a range of reactions includinghydroformylations. Also once absorbed, the spectrum of the aerogel ischanged so that the aerogel can be used as a detector for the presenceof the gases. This detection can be done by optical spectroscopy in theinfrared, visible or ultraviolet regions, light scattering by Raman, orother dispersive or non-dispersive methods, by spin resonancespectroscopy using electron or nuclear spins, or by magneticinteractions. Thus, the changes that the aerogels undergo when theyinteract with gas molecules or other molecules can be detected by thesemeans. In addition to changes in light transmission, the magneticchanges that result from the oxidation or reduction of the adsorbate orabsorbent are observable magnetically. It is known that aerogelscomprising silica are useful in some forms of particle detection, suchas Chrenkov radiation detectors. The incorporation of the organicpolymers and metal ions selected from a broad group of metals provides anew class of particle detectors whose advantage is in the metal specificinteractions with the particles.

The optical properties of the aerogels are novel in that they reflectthe presence of the metal ions (as well as those of the silica andpolymer) and so they may be utilized as detector elements for thepresence of species that are absorbed by the aerogel and so can beobserved through their presence in that environment by spectroscopicmeans. Another novel feature of the aerogels is that the metal ionproperties can be obtained in a clear monolithic structure with a lowrefractive index. This provides a new medium for optical elements.

The high absorbance of liquids by the aerogels tested and their apparentability to mordant dyes contained in the liquids, has been shown to makethe aerogels, either in monolithic or particulate form, suitable fortheir use in imaging systems. Thus, the use of these materials in thecoating on the imaging layer of paper, could produce a rapid dryingagent to absorb ink and analogous fluids from other imaging systems.

Based on the behavior of the aerogels containing rodium, ruthenium,platinum, and palladium, and the field of catalysis using species ofthese elements on high surface area supports, it is contemplated thatthe materials of this invention will function as catalysts for manyreactions beyond those demonstrated. The catalysts of the FischerTropsch reaction, the reduction of nitrogen oxides, and the oxidation ofCO, and the oxidation of nitrogen oxides are particularly contemplated.

Table 2 set forth below, lists physical properties for several preferredembodiment silica-chitosan aerogels in accordance with the presentinvention.

TABLE 2 Physical Properties of Transition Metal ContainingSilica-Chitosan Aerogels Density Refractive lndex* BET Surface SampleName (g/cm³) (632.8 nm) Area (m²/g) Silica-Chitosan ~0.25 1.14 550–600Aerogel (Silica-X) Co (II) Containing ~0.26 1.14 500–800 Silica-XAerogel Rh (III) Containing ~0.27 1.17 550–950 Silica-X Aerogel Ru (III)Containing ~0.27 1.17 500–800 Silica-X Aerogel *Refractive indices aremeasured at 632.8 nm with Metricon (Model 2010) Prism Coupler

The aerogels prepared by the methods of this invention are useful forabsorbing and extracting metal ion containing species from solutions.

The examples showing the uptake of metal ions in the function of thesol-gels, followed by super critical extraction, and then theirconversion to dense glassy materials at 800° C., shows that the methodsprovide an improved way to encapsulate metal ions such as those fromnuclear waste. The high temperature step of this process involves theloss of a very small mass of volatiles relative to the mass of themetals taken up in comparison to conventional sol-gel processes. Itinvolves low temperature glass formation to obtain silica compositesrelative to conventional melt-quench methods.

The invention has been described with reference to the preferredembodiments. Obviously, modifications and alterations will occur toothers upon a reading and understanding the preceding detaileddescription. It is intended that the invention be construed as includingall such modifications and alterations in so far as they come within thescope of the appended claims or the equivalents thereof.

1. An aerogel particle for use on an imaging surface, said aerogelparticle comprising silica, at least one organic polymer with a polarfunctional group, and at least one metal-ion-containing species, whereinthe polar functional group of the organic polymer is selected from thegroup consisting of amine, carbonyl, acylamine, protonated amine,hydroxyl, and carboxyl groups, wherein the polymer is selected from thegroup consisting of a chitosan with a deacylation degree 50 to 100%pectic acid, and alginic acid, and wherein the metal is selected fromthe group consisting of Co, Cu, Fe, Cr, Ni, Mn, Rh, Ru, Ir, Pd, Pt, Yb,Er, Eu, Sm, and Dy.
 2. The aerogel particle of claim 1, wherein themetal is a metal ion having an oxidation state from one to six.
 3. Theaerogel particle of claim 1, further comprising at least one absorbeddye.
 4. An aerogel for use as an ink pigment on imaging surfacescomprising aerogel particles, wherein said aerogel particles comprise:silica; chitosan; and, an absorbed dye.
 5. The aerogel of claim 4,wherein said aerogel particles have a minimum particle size of about 25nanometers.
 6. The aerogel particles of claim 4, further comprising ametal-ion-containing species.
 7. The aerogel particles of claim 4,wherein the chitosan has an average molecular weight of from about35,000 to about 3,000,000.
 8. Aerogel particles for use on an imagingsurfaces, comprising silica, at least one organic polymer with a polarfunctional group, and at least one metal-ion-containing species, whereinthe polar functional group of the organic polymer is selected from thegroup consisting of amine, carbonyl, acylamine, protonated amine,hydroxyl, and carboxyl groups, wherein the polymer is selected from thegroup consisting of a chitosan with a deacylation degree 50 to 100%.pectic acid, and alginic acid, and wherein the metal is selected fromthe group consisting of Go, Cu, Fe, Cr, Ni, Mn, Rh, Ru, Ir, Pd, Pt, Yb,Er, Eu, Sm, and Dy.
 9. The aerogel particles of claim 8, wherein theaerogel particles have a minimum size of about 25 nanometers.
 10. Theaerogel particles of claim 8, wherein the metal is a metal ion having anoxidation state from one to six.
 11. The aerogel particle of claim 8,further comprising at least one absorbed dye.